Fuel cells for combining hydrogen and oxygen to produce electricity are well known. A known class of fuel cells includes a solid oxide electrolyte layer through which oxygen anions migrate; such fuel cells are referred to in the art as “solid-oxide” fuel cells (SOFCs).
In some applications, for example, as an auxiliary power unit (APU) for an automotive vehicle, an SOFC stack assembly is preferably fueled by “reformate” gas, which is the effluent from a catalytic gasoline oxidizing reformer. Reformate typically includes amounts of carbon monoxide (CO) as fuel in addition to molecular hydrogen. The reforming operation and the fuel cell operation may be considered as first and second oxidative steps of the liquid hydrocarbon, resulting ultimately in water and carbon dioxide. Both reactions are exothermic, and both are preferably carried out at relatively high temperatures, for example, in the range of 650° C. to 900° C.
A complete fuel cell stack assembly comprises a plurality of components and sub-assemblies joined together mechanically to provide the desired flow paths and control pathways for the reactive gases, spent gases, and cooling gases. It is essential that the joints or interfaces between the components and sub-assemblies be durably leak-free at temperatures from below 0° C. to as high as at least 900° C., at pressures from subatmospheric to up to several atmospheres. Such conditions place very high demands on materials selected for gaskets at these joints and interfaces.
It has been proposed to use various glass and ceramic compositions as SOFC sealants, based on boron, phosphate, and silica, as referenced in U.S. Pat. No. 6,430,966. These glass/ceramic sealants are also useful as dielectric insulators between adjacent cell elements at different voltage potentials. However, these sealants have some known drawbacks.
At operating temperatures, phosphate glasses are too volatile and react with the anode material to form various nickel phosphorous compounds. They also show low stability in humidified fuel gas. Borosilicates are known to react with a humidified hydrogen atmosphere to form the gaseous species B2(OH)2 at operating temperature, and thus the seal corrodes with time.
Typically, glass seals require high-temperature heat treatment (700° C.-900° C.) during manufacture of a fuel cell system, during which the glass softens and flows to fill the interface between the components and bonds to the surfaces. Upon further heating and increased time, the melt devitrifies to form the final microstructure desired for the application. This seal provides a good insulating joint and a good initial bond joint. The seal functions satisfactorily until the stack assembly undergoes multiple thermal cycles when it becomes prone to crack propagation. Because of localized differences in the coefficients of thermal expansion of the components and the glass seals, and because the glass may be progressively crystallized, the seal may fracture, resulting in gas leakage and failure of the fuel cell stack assembly. As the leak increases progressively, cell output diminishes until the total voltage output is unacceptably low.
A material used in forming sealing gaskets known in the prior art, as disclosed in U.S. Pat. No. 6,430,966, is a silicate based glass that exhibits high chemical resistance and minimal interaction with other fuel cell materials. A known material for such use is a blend of metal (M) oxides, MAOX+MBOY+SiO2, wherein MA may be barium, strontium, calcium, or a combination thereof and MB may be aluminum, boron, phosphorus, gallium or lead, or a combination thereof. MBOY modifies the softening temperature of the glass and the combination of MAOX and SiO2 offers an improved coefficient of thermal expansion.
The material also provides good insulation and a good initial bond joint. However, it is prone to micro-cracking at low temperatures, increased brittleness with time during operation, and loss of bond strength with thermal cycles. Therefore, it can be difficult to maintain an adequate seal during repeated thermal cycling.
Glass seals made of compositions known in the art are also commonly prone to process variation. When fabricated from tape cast film that includes a glass frit and an organic binder, seal space can be difficult to control. This is because, during the initial heating of the SOFC stack, the binder burns out and a significant amount of shrinkage occurs. Depending on the compressive load, time under load, and heating/cooling rates in the application, it is difficult to reproduce the structure of the crystallized glass with each fabricated stack assembly. Further, flow properties of the material are very sensitive to average particle size and particle size distribution of the glass frit which is the precursor powder for the glass joint.
What is needed is a material for gasketing in an SOFC system which is thermally stable over the range between shutdown and operating temperatures for both the reformer and the fuel cell assembly; which is chemically stable in oxidizing and reducing environments; which is acceptably rugged for assembly and operation of the system; which can provide a dielectric function; which matches the coefficient of thermal expansion of stainless steel elements in the fuel cell assembly; and which is compatible with other materials of the system.
It is a principal object of the present invention to provide an improved material for hermetic sealing and electrically insulating gasketing joints in a fuel cell assembly.